BR112018008631B1 - OPTICAL ARTICLE THAT PROTECTS FROM BLUE AND UV LIGHT - Google Patents

Abstract

OPTICAL ARTICLE THAT PROTECTS FROM BLUE AND UV LIGHT. The present invention relates to an optical article comprising a substrate having a front main face and a rear main face, having a colorimetric coefficient b* as defined in the international colorimetric system L*a*b* CIE (1976) which is less than or equal to to 7, a relative light transmission factor in the visible spectrum Tv greater than or equal to 87%, blocking at least 8% of light having a wavelength varying between 420 and 450 nm reaching said front main face, and having a factor of average RUV reflection on said rear main face between 280 nm and 380 nm, weighted by the function W(é) defined in ISO 13666:1998, less than 7% for both an angle of incidence of 30° and an angle of incidence of 45°. This optical article can be used to protect a user's eyes against UV light and phototoxic blue light.

Description

[0001] The present invention relates to the field of optics, more particularly to an optical article, preferably an ophthalmic lens, preferably having a low level of yellow tint, in particular a mainly colorless appearance and being perceived as having good transparency. , while comprising optical means for blocking at least part of the phototoxic blue light and protecting from UV light.

[0002] Visible light as perceived by humans approximately spans a spectrum ranging between a wavelength of 380 nm and a wavelength of 780 nm, and more specifically between 400 and 700 nm. The part of this spectrum, ranging between about 380 nm and about 500 nm, corresponds to essentially high-energy blue light.

[0003] Many studies (see, for example, Kitchel E., “The effects of blue light on ocular health,” Journal of Visual Impairment and Blindness Vol. 94, No. 6 , 2000 or Glazer-Hockstein et al., Retina, Vol. 26, No. 1, pages 1 to 4, 2006) suggest that part of blue light has phototoxic effects on the health of the human eye and especially on the retina.

[0004] The ISO 8980-3:2003 (E) Table B1 defines the blue light hazard function B(À).

[0005] Studies of ocular photobiology (Algvere P. V. et al., “Age-Related Maculopathy and the Impact of the Blue Light Hazard”, Acta Ophthalmo. Scand. , Vol. 84, pp. 4-15, 2006) and clinical trials (Tomany S. C. et al., “Sunlight and the 10-Year Incidence of Age-Related Maculopathy. The Beaver Dam Eye Study.” of Age-Related Maculopathy. The Beaver Dam Eye Study), Arch Ophthalmol., Vol. 122. pp. 750 to 757, 2004) demonstrated that excessively prolonged or intense exposure to blue light can induce ophthalmic diseases serious conditions, such as age-related macular degeneration (AMD) or cataracts.

[0006] Another recent publication Arnault E., Barrau C., Nanteau, C. Gondouin P., Bigot K., Vienot F., Gutman E., Fontaine V., Villette T., Cohen-Tannoudji D., Sahel J.A. , Picaud S.: “Phototoxic action spectrum on a retinal pigment epithelium model of age-related macular degeneration exposed to sunlight normalized conditions” of sunlight), Aug 23, 2013, PLOS One, Aug 23, 2013;8(8):e71398. doi: 10.1371/journal.pone.0071398. eCollection 2013 defined the precise spectrum of retinal toxicity of light under physiological irradiation conditions in an in vitro model of age-related macular degeneration using primary cultures of porcine retinal pigment epithelium cells incubated for 6 hours with different concentrations of a photosensitive derivative of the visual pigment, N-retinylidene-N-retinylethanolamine (A2E).

[0007] Therefore, it is recommended to limit exposure to potentially harmful blue light, in particular in relation to the wavelength band with greater danger described in the documents above.

[0008] Furthermore, the solar spectrum comprises electromagnetic radiations having various wavelengths, especially ultraviolet (UV) radiation. The UV spectrum has many bands, especially UVA, UVB and UVC bands. Among the UV bands that reach the Earth's surface, the UVA band, ranging between 315 nm and 380, and the UVB band, ranging between 280 nm and 315 nm, are particularly harmful to the retina.

[0009] Traditional anti-reflective coatings are designed and optimized to reduce reflection on the surface of the lens in the visible region, typically within the spectrum range of 380 to 780 nm. As a rule, reflection in the ultraviolet region (280 to 380 nm) is not optimized, and is often reinforced by the traditional anti-reflective coating itself. The article “Anti-reflective coatings reflect ultraviolet radiation”, Citek, K. Optometry 2008, 79, 143 to 148 highlights this phenomenon.

[0010] The average reflection in the UVA and UVB regions can therefore reach high levels (up to 60%) for traditional anti-reflective lenses. For example, for non-solar anti-reflective articles that are marketed by most manufacturers during recent years, the average UV reflection varies between 10 and 25% for an incidence angle of 30 to 45°. This is not problematic on the front face of the lens, since most of the UV radiation coming from the front of the wearer that can reach the wearer's eye (normal incidence, 0 to 15°) is generally absorbed by the ophthalmic lens substrate. Better protection against the transmission of UV radiation can be obtained through solar ophthalmic lenses, which are studied and designed to reduce visible spectrum luminosity, fully absorb UVB and totally or partially absorb UVA.

[0011] On the other hand, UV radiation resulting from light sources located behind the wearer can reflect on the back face of the lens and reach the wearer's eye if the lens is not equipped with an anti-reflective coating that is efficient in the ultraviolet region, affecting thus potentially harming the health of the wearer. This phenomenon is made stronger by the trend toward fashionable sunglasses with high diameters that increase the risk of stray reflections entering the eyes.

[0012] It is assumed that the light rays that may reflect on the back face of the lens and reach the wearer's eye have a narrow incidence angle range, varying between 30 and 45° (oblique incidence).

[0013] Therefore, it may be advisable for a wearer of glasses to wear an ophthalmic lens in front of each eye that prevents or limits the transmission of phototoxic blue light to the retina, and that strongly reduces reflection in the range of UVA and UVB radiation. on the back face. These lenses can also provide greater visual performance due to greater contrast sensitivity.

[0014] Application WO 2012/076714, in the name of the applicant, discloses an ophthalmic lens comprising a substrate having a front main face and a rear main face, said rear main face being coated with a multi-layer anti-reflective coating having good properties anti-reflection in both the visible spectrum and the UV range, i.e. an average RUV reflection factor on said back face between 280 nm and 380 nm, weighted by the function W(À) defined in the ISO 13666:1998 standard, which is less than 5 %, for an angle of incidence of 30° and for an angle of incidence of 45°.

[0015] Likewise, it has been suggested, for example in patent application WO 2008/024414, to cut at least partially the problematic part of the blue light spectrum from 400 nm to 460 nm, by means of lenses comprising a film partially inhibiting the light in the appropriate wavelength range, through absorption or through reflection. This can also be accomplished by incorporating a yellow absorbent dye into the optical element.

[0016] US Patent 8360574 discloses an ophthalmic lens comprising a selective light wavelength filter that blocks 5 to 50% of light having a wavelength in the range of 400 to 460 nm, transmits at least 80% of the light having a wavelength in the range of 460 to 700 nm and exhibits a yellow hue index of no more than 15.

[0017] Application WO 2014/133111 discloses an optical material containing one or more ultraviolet absorbers having a maximum absorption peak in a range of 350 nm to 370 nm, which is configured to restrict exposure of a user's eyes to light blue with relatively short wavelengths, specifically in the wavelength range of 400 to 420 nm.

[0018] Application WO 2013/084177 describes an optical device comprising an optical substrate provided with selective optical filtering means configured to selectively inhibit the transmission, through the optical substrate, of at least a selected range of wavelengths, having a width of bandwidth in a range of 10 nm to 70 nm centered on a wavelength between 430 nm and 465 nm, of incident light in the visible light spectrum at an inhibition rate of at least 5%, the selective optical filtering means being further configured to transmit at least 8% of incident light of the visible spectrum outside said at least one selected range of wavelengths.

[0019] Lenses with an anti-reflective coating partially rejecting harmful blue visible light have been released onto the market. They maintain a high level of transmission (greater than 97%), since their anti-reflective coating has a low reflectance in the visible range. At this level of transparency, the carrier is sensitive to a small loss of transmission, and the current trend is to increase transmission, that is, transparency.

[0020] Considering the above, there is a need for an optical article capable of at least partially blocking harmful blue and protecting from harmful UV light, while maintaining good transparency and good aesthetics based on the perception of the user or wearer.

[0021] It is also desirable that the optical article selectively blocks a relatively narrow range of the blue spectrum, that is, blocks only the part of the blue spectrum that is harmful to the eye, and exhibits a low level of yellow tint. The optical article should be perceived as mostly colorless by an external observer.

[0022] Another objective, when the optical article is an ophthalmic system, is to obtain both satisfactory protection of the wearer against harmful wavelengths and satisfaction of the wearer. In this regard, the optical article must provide high comfort to the wearer in terms of visibility. An acceptable overall level of light transmission is equally necessary, as well as an acceptable color perception for a user, i.e., the optical article must not drastically impair the wearer's color vision, and preferably the lens has anti-glare and/or anti-glare properties. contrast enhancement.

[0023] The present inventors have discovered that these objectives can be achieved by providing an optical article with a lower transmission, but, in return, having a better yellow tint level, i.e., a reduced yellow tint level for light transmitted through the optical article. The combination of these properties leads to better acceptability of the optical article by the user. This finding is contrary to general knowledge in the field of ophthalmic optics, in which it is usually considered that the best clear lens is the lens with the highest transmission. In fact, the experimental part demonstrates that the lenses considered to be the most transparent for users are those with the lowest residual yellow tone, even if they have to have a slightly lower transmittance in the visible spectrum to achieve this result.

[0024] The unexpected discovery that a carrier was much more sensitive to an increase in color than to a decrease in transmittance caused the present inventors to propose new optical articles.

[0025] To meet the needs of the present invention and to remedy the aforementioned disadvantages of the prior art, the applicant provides an optical article comprising a substrate with a front main face and a rear main face, having a colorimetric coefficient b* as defined in international colorimetric system L*a*b* CIE (1976) which is less than or equal to 7, a relative light transmission factor in the visible spectrum Tv equal to or greater than 87%, blocking at least 8% of light having a length of wave varying between 420 and 450 nm arriving at said front main face, and having an average reflection factor RUV at said rear main face between 280 nm and 380 nm, weighted by the function W(À) defined in ISO 13666:1998, lower at 7% for an incidence angle of 35° (on the back face). In another embodiment, RUV on said rear main face between 280 nm and 380 nm, weighted by the W(À) function defined in ISO 13666:1998, is less than 7% for both an incidence angle of 30° and an angle incidence of 45°.

[0026] As used herein, when an article comprises one or more layers or one or more coatings on the surface thereof, "depositing a layer or a coating on the article" means that a layer or a coating is deposited on the uncovered (exposed) surface. the outer coating of the article, i.e. the coating that is furthest from the substrate.

[0027] As used herein, a coating that is “on” a substrate/coating or that has been deposited “on” a substrate/coating is defined as a coating that (i) is positioned on top of the substrate/coating, ( ii) is not necessarily in contact with the substrate/coating, i.e. one or more intermediate coatings may be sandwiched between the substrate/coating and the relevant coating (although it is preferably in contact with said substrate/coating) and ( iii) does not necessarily completely cover the substrate/coating. When “a coating 1 is said to be located under a coating 2”, it must be understood that coating 2 is further from the substrate than coating 1.

[0028] In the present description, unless otherwise specified, an optical article is understood to be transparent when observation of an image through said optical article is perceived by a wearer and/or an observer without adversely affecting the quality of the image. This definition of the term “transparent” may apply to all objects qualified as such in the description, unless otherwise specified.

[0029] The optical article according to the invention is preferably a transparent optical article, in particular an optical lens or a lens glass, more preferably an ophthalmic lens or a lens glass.

[0030] The term “ophthalmic lens” is used to mean a lens adapted to a spectacle frame to protect the eye and/or correct vision. Said lens can be chosen from afocal, unifocal, bifocal, trifocal and progressive lenses. Although ophthalmic optics is a preferred field of the invention, it will be understood that this invention may apply to optical elements of other types where filtering blue wavelengths may be beneficial, such as lenses for optical instruments, filters particularly for photography or astronomy, optical vision lenses, ocular displays, lighting system optics, screens, glazing, etc.

[0031] The optical article preferably comprises a substrate and at least one layer coated on the substrate. If it is an optical lens, it may be coated on its front main surface, on its rear main surface, or on both sides. As used herein, the back face of the substrate is intended to mean the face which, using the article, is closest to the wearer's eye. Generally, it is a concave face. On the contrary, the front face of the substrate is the face that, when using the article, is furthest from the wearer's eye. Generally, it is a convex face. The optical article may also be a flat article.

[0032] A substrate, in the sense of the present invention, should be understood to mean an uncoated substrate, and generally has two main faces. The substrate may, in particular, be an optically transparent material having the shape of an optical article, for example an ophthalmic lens intended to be mounted on spectacles. In this context, the term “substrate” is understood to mean the base constituent material of the optical lens and, more particularly, the ophthalmic lens. This material functions as a support for the stack of one or more coatings or layers.

[0033] The substrate of the article of the invention may be a mineral or organic substrate, for example an organic substrate made of a thermoplastic or thermosetting plastic, generally chosen from ophthalmic grade transparent materials used in the ophthalmic industry.

[0034] Especially preferred classes of substrate materials are polycarbonates, polyamides, polyimides, polysulfones, copolymers of polyethylene terephthalate and polycarbonate, polyolefins, such as polynorbornenes, resins resulting from polymerization or (co)polymerization of alkylene glycol bis allyl carbonates, such as diethylene glycol bis(allylcarbonate) polymers and copolymers (marketed, for example, under the name CR-39® by the company PPG Industries, the corresponding marketed lenses being referred to as ORMA® lenses from ESSILOR), polycarbonates, e.g. bisphenol-A derivatives, (meth)acrylic or thio(meth)acrylic polymers and copolymers, such as polymethyl methacrylate (PMMA), urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, episulfide polymers and copolymers.

[0035] The optical article according to the invention blocks or cuts at least 8% of the light having a wavelength ranging between 420 and 450 nm reaching said front main face, preferably at least 12%. In the present application, “blocking X %” of incident light in a specified wavelength range does not necessarily mean that some wavelengths within the range are completely blocked, although this is possible. Instead, “blocking X %” of incident light within a specified wavelength range means that an average of X % of said light within the range is not transmitted. As used herein, light blocked in this way corresponds to light arriving at the front main face of the optical article.

[0036] This attenuation of the electromagnetic spectrum at wavelengths in the range specified above may correspond to at least 20%; or at least 30%; or at least 40%; or at least 50%; or at least 60%; or at least 70%; or at least 80%; or at least 90%; or at least 95%; or at least 99%; or 100%. In one embodiment, the amount of light having a wavelength ranging between 420 and 450 nm blocked by the optical article varies between 8 and 50%, more preferably between 10 and 40%, even more preferably between 12 and 30%.

[0037] The optical article according to the invention has a relative light transmission factor in the visible spectrum Tv equal to or greater than one of the following values: 87%, 88%, 89%, preferably equal to or greater than 90%, more preferably equal to or greater than 92%, and better equal to or greater than 95%. Said Tv factor preferably varies between 87% and 98.5%, more preferably between 87% and 97%, even better between 87% and 96%. In another modality, Tv varies between 89% and 98%, preferably between 90% and 97%.

[0038] Preferably, and in general, said Tv value is less than 99%, preferably equal to or less than 98.5%, even better equal to or less than 98%. In another preferred embodiment, Tv is equal to or less than 97.5%, and better equal to or less than 97%. The Tv factor, also called “light transmission” of the system, is as defined in the NF EN 1836 standard and relates to an average in the wavelength range from 380 to 780 nm that is weighted according to the sensitivity of the eye in each gamma wavelength and measured in D65 (daylight) lighting conditions.

[0039] The optical article according to the invention has a colorimetric coefficient b* as defined in the international colorimetric system L*a*b* CIE (1976) which is less than or equal to 7, preferably equal to or less than the following values: 6 %, 5%, more preferably equal to or less than 4, 3.5, 3, 2.5, 2. The low colorimetric coefficient b* of the optical article can be correlated with its limited or non-yellow appearance. In fact, positive values on the b* axis indicate amounts of yellow, while negative values indicate amounts of blue.

[0040] The optical article according to the invention has a colorimetric coefficient a* as defined in the international colorimetric system L*a*b* CIE (1976) preferably equal to or greater than -5, and preferably less than 1, and preferably varies between -5 and -1, preferably varies between 0 and -2.5.

[0041] The above colorimetric coefficients are calculated between 380 and 780 nm for light transmitted through the lens at an angle of incidence varying between 0 and 15°, especially 0°, using standard observer 10° and standard illuminant D65.

[0042] In some embodiments, the optical article comprises at least one optical filtering means that at least partially blocks incident light having a wavelength ranging between 420 and 450 nm (blue light), i.e., inhibits transmission in the range phototoxic spectral through at least one geometrically defined surface of the substrate of the optical article, preferably an entire main surface. In the present description, unless otherwise specified, light blocking is defined with reference to an angle of incidence varying between 0° and 15°, preferably 0°.

[0043] According to the invention, the angle of incidence corresponds to the angle formed by a ray of light incident on an ophthalmic lens surface and a perpendicular to the surface at the point of incidence. The light ray is, for example, an illuminant light source, such as standard illuminant D65 as defined in the international colorimetric L*a*b* CIE. Generally, the angle of incidence changes from 0° (normal incidence) to 90° (grazing incidence). The usual range of incidence angles is 0° to 75°.

[0044] In the present description, the optical filtering means may be an absorption filter that blocks the transmission of light by absorption, an interference filter that blocks the transmission of light, for example, by reflection, or a combination of both ( i.e. a filter that is both absorption and interference). The optical article may also comprise at least one absorption filter and at least one interference filter, both of which at least partially block incident light having a wavelength ranging between 420 and 450 nm. Using an interference filter in addition to an absorption filter can improve the aesthetics of the optical article.

[0045] In another embodiment, the optical article comprises at least one interference filter that at least partially blocks incident light having a wavelength ranging between 420 and 450 nm on at least one geometrically defined surface of the substrate of the optical article, preferably an entire main surface, within a first selected range of angles of incidence. The interference filter, preferably a filter that inhibits the transmission of light by reflection in the range of 420 to 450 nm, generally corresponds to a multilayer dielectric stack, typically manufactured by depositing distinct layers of alternating high and low refractive index materials. Design parameters, such as individual layer thickness, individual layer refractive index and number of layer repetitions, determine the performance parameters for multilayer dielectric stacks. Such an interference filter inhibiting light in the range of 420 to 450 nm is disclosed, for example, in application WO 2013/171434, and WO 2013/171435 in the name of the applicant, incorporated herein by reference.

[0046] In a preferred embodiment, the optical article comprises at least one absorption filter. In this case, the optical filtering medium can be selected from an absorbent dye and/or a UV absorber. As used herein, an absorbent dye can refer to both a pigment and a colorant, that is, it can be respectively insoluble or soluble in its vehicle.

[0047] Preferred absorption filters have a narrow absorption band in the range of 420 to 450 nm of the electromagnetic spectrum. Ideally, said absorption band is centered at about 430 nm. Preferably, they do not absorb, or absorb very little (typically less than 5%, preferably less than 4%, more preferably less than 3%) in regions of the visible spectrum outside the wavelength range of 410 to 450 nm.

[0048] Preferably, the optical filtering medium selectively inhibits light within the range of 420 nm to 450 nm. As used herein, a medium “selectively inhibits” a wavelength range if it inhibits at least some transmission within the range of 420 to 450 nm, while having little or no effect on the transmission of visible wavelengths outside the range of wavelength unless specifically configured to do so.

[0049] In fact, the optical filtering medium can be configured to inhibit, to a certain extent, the transmission of incident light of wavelengths outside the range of 420 to 450 nm, usually by absorption.

[0050] In some cases, it may be particularly desirable to selectively filter a relatively small portion of the blue spectrum, i.e. the region from 420 nm to 450 nm. In fact, it has been discovered that blocking too much of the blue spectrum can interfere with scotopic vision and mechanisms for regulating biorhythms, referred to as “circadian cycles.” Thus, in a preferred embodiment, the optical filtering means blocks less than one of the following values 5%, 4%, 3%, 2%, more preferably 1% of the light having a wavelength ranging between 465 and 495 nm, preferably between 450 and 550 nm, reaching the main front face of the optical article. In this embodiment, the optical filtering medium selectively blocks phototoxic blue light and transmits blue light implicated in circadian rhythms.

[0051] Preferably, the optical article transmits at least 95% of light having a wavelength ranging between 465 and 495 nm. This transmittance corresponds to an average of transmitted light within the range of 465 to 495 nm that is not weighted according to the sensitivity of the eye at each wavelength in the range. In another embodiment, the optical filtering medium does not absorb light in the range of 465 to 495 nm, preferably in the range of 450 to 550 nm.

[0052] In a preferred embodiment, the optical filtering means is configured so that the optical transmittance of the optical article satisfies at least one of characteristics (1) to (3) below and preferably these three characteristics: a. optical transmittance at a wavelength of 435 nm corresponds to 10% or less; B. optical transmittance at a wavelength of 450 nm corresponds to 70% or less; w. optical transmittance at a wavelength of 480 nm corresponds to 80% or more;

[0053] In the case of an absorption filter, these characteristics can be achieved using appropriate absorbent dyes and/or UV absorbers in a suitable concentration.

[0054] In the present description, unless otherwise specified, the transmittances/transmissions are measured in the center of the optical article in relation to a thickness varying between 0.7 and 2 mm, preferably between 0.8 and 1.5 mm, in a angle of incidence varying between 0° and 15°, preferably 0°. As used herein, transmitted light refers to light arriving at the front main face of the optical article and passing through the lens.

[0055] The chemical nature of the absorbent dye that can function as a means to at least partially inhibit light having a wavelength ranging between 420 and 450 nm is not particularly limited, as long as it has an absorption peak, ideally an absorption peak maximum, within the range of 420 to 450 nm. The LMA (Width at Half Height) is preferably less than 40 nm, preferably less than 30 nm.

[0056] Blue light blocking dyes, typically yellow dyes, may include one or more dyes from the group consisting of: auramine O; coumarin 343; coumarin 314; nitrobenzoxadiazole; yellow Lucifer CH; 9,10- bis(phenylethynyl)anthracene; proflavine; 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran; 2-[4-(dimethylamino)styryl]-1-methypyridinium iodide, lutein and zeaxanthin.

[0057] In embodiments, the absorbent dye comprises one or more porphyrins, one or more porphyrin complexes, other heterocycles related to porphyrins, including corrins, chlorins and corfins, derivatives thereof, or the perylene, coumarin, acridine, indolenine families ( also known as 3H-indole) and indole-2-ylidene. Derivatives are substances generally produced by an addition or substitution.

[0058] Porphyrins correspond to well-known macrocycle compounds composed of four modified pyrrole subunits interconnected at their carbon atoms via methine bridges. The main porphyrin corresponds to porphin and the substituted porphins are called porphyrins. Porphyrins correspond to the conjugated acids of ligands that join metals to form (coordination) complexes.

[0059] Certain porphyrins or certain porphyrin complexes or derivatives are interesting since they provide selective absorption filters having a bandwidth in some cases of, for example, 20 nm in the selected range of wavelengths. The property of selectivity is in part provided by the symmetry of the molecules. This selectivity helps to limit distortion of visual color perception, to limit the harmful effects of light filtering on scotopic vision, and to limit the impact on circadian rhythm.

[0060] For example, one or more porphyrins or one or more porphyrin complexes or derivatives are selected from the group consisting of Chlorophyll a; Chlorophyll b; 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin sodium salt complex; 5,10,15,20-tetrakis(N-alkyl-4-pyridyl) porphyrin complex; 5,10,15,20-tetrakis(N-alkyl-3-pyridyl) porphyrin complex and 5,10,15,20-tetrakis(N-alkyl-2-pyridyl) porphyrin complex, the alkyl preferably being a chain alkyl, linear or branched, comprising 1 to 4 carbon atoms per chain. For example, alkyl may be selected from the group consisting of methyl, ethyl, butyl and propyl.

[0061] Usually, the complex is a metal complex, the metal being selected from the group consisting of Cr(III), Ag(II), In(III), Mn(III), Sn(IV), Fe(III ), Co(II), Mg(II) and Zn(II). Cr(III), Ag(II), In(III), Mn(III), Sn(IV), Fe(III), Co(II) and Zn(II) demonstrate absorption in water in the range of 425 nm to 448 nm with sharp absorption peaks. Furthermore, the complexes provided are stable and not sensitive to acid. Cr(III), Ag(II), In(III), Sn(IV), Fe(III), in particular, do not exhibit fluorescence at room temperature, which is a useful property in optical lenses, e.g. ophthalmic lenses. .

[0062] In some embodiments, one or more porphyrins or one or more porphyrin complexes or derivatives are selected from the group consisting of meso-tetra(4-sulfonatophenyl) magnesium porphine tetrasodium salt, magnesium octaethylporphyrin, magnesium tetramesitylporphyrin , octaethylporphyrin, tetrakis porphyrin (2,6-dichlorophenyl), tetrakis porphine (o-aminophenyl), tetramesitylporphyrin, tetraphenylporphyrin, zinc octaethylporphyrin, zinc tetramesitylporphyrin, zinc tetraphenylporphyrin and diprotonated tetraphenylporphyrin.

[0063] In one embodiment, the optical filtering means at least partially blocking light having a wavelength ranging between 420 and 450 nm is a UV absorber. These compounds are often incorporated into optical articles in order to reduce or prevent UV light from reaching the retina (particularly in ophthalmic lens materials). The UV absorber that can be used in the present invention preferably has the ability to at least partially block light having a wavelength less than 400 nm, preferably UV wavelengths below 385 or 390 nm, but also has an absorption spectrum extending into the visible blue light range (400 to 500 nm). Most preferred ultraviolet absorbers have a maximum absorption peak in a range of 350 nm to 370 nm and/or do not absorb light in the range of 465 to 495 nm, preferably in the range of 450 to 550 nm.

[0064] Said UV absorbers protect both the user's eye against UV light and the substrate material itself, thus preventing it from deteriorating and becoming brittle and/or yellow.

[0065] The UV absorber is preferably a benzotriazole compound. Suitable UV absorbers include, without limitation, 2-(2-hydroxyphenyl)-benzotriazoles, such as 2-(2-hydroxy-3-t-butyl-5-methylphenyl) chlorobenzotriazole, 2-(2' -hydroxy-5'-t-octylphenyl), 2-(3'-metalyl-2'-hydroxy-5'-methyl phenyl) benzotriazole or other allylhydroxymethylphenyl benzotriazoles, 2-(3,5-di- t-amyl-2-hydroxyphenyl), and the 2-hydroxy-5-acryloxyphenyl-2H-benzotriazoles disclosed in U.S. Patent No. 4,528,311. Preferred absorbers are from the benzotriazole family. Commercially available products include Tinuvin 326 from BASF, Seeseorb 703 from Cipro, Viosorb 550 from Kyodo Chemicals and Kemisorb 73 from Chemipro. TCP (Tinuvin Carbo Protect) is a good candidate.

[0066] The UV absorber is preferably used in an amount representing 0.3 to 2% of the weight of the substrate.

[0067] According to a preferred embodiment, the optical filtering means absorbs radiation such that at least 8% of the light having a wavelength ranging between 420 and 450 nm arriving at said front main face is blocked/inhibited, preferably at least 12%, and generally 8 to 50%, more preferably between 10 and 50%, even more preferably ranging between 12 and 50% or between 10 and 40%, even more preferably between 12 and 30% of said light. These levels of light absorption inhibition can be controlled by adjusting the concentration of the absorbing dye and/or UV absorber and are expressed relative to the amount of light that would be transmitted in the same wavelength range in the absence of the optical filtering medium.

[0068] Generally, blocking undesirable blue light wavelengths affects color balance, color vision if a person looks through the optical device, and the color in which the optical device is perceived. In fact, blue light blocking optical devices incorporating at least one of the above-described absorption optical filtering means that at least partially inhibit light having a wavelength ranging between 420 and 450 nm have a tendency to produce a color cast. in the optical article as a “side effect”, the latter appearing yellow, brown or amber in color. This is aesthetically unacceptable for many optical applications, and may interfere with the user's normal color perception if the device is an ophthalmic lens.

[0069] To compensate for the yellowing effect of the blue light blocking filter and obtain an optical article having a cosmetically acceptable appearance when viewed by an external observer, in particular perceived as mainly neutral in color, the optical article comprises, in an embodiment, at least one color balance component, when it is desired to obtain a colorless appearance.

[0070] In one embodiment, the color balancing component employed to at least partially compensate for the yellowing effect corresponds to a dye, such as a blue dye dye, or a mixture of dyes used in suitable proportions, such as a combination of red and green dye dyes.

[0071] Color balancing dyes are typically incorporated into a color balancing film or coating applied to the surface of the optical article, such as a primer coating, hard coating or anti-reflective coating.

[0072] Examples of fixed tone colorants may include any of the organic and inorganic dyes and/or pigments recognized in the art. Organic dyes can be selected from azo dyes, polymethine dyes, arylmethine dyes, polyene dyes, anthracenedione dyes, pyrazolone dyes, anthraquinone dyes, auinophthalone dyes and carbonyl dyes. Specific examples of these organic dyes include Blue 6G, Violet PF, and Magenta RB available from Keystone Aniline, Morplas Blue from Morton International, Inc., D&C Violet 2 available from Sensient Corp., Macrolex 3R Violet from Lanxess, and Rubine Red from Clariant Corporation. Equally suitable are laser dyes, for example those selected from pyrromethene, fluorscein, rhodamine, malachite green, oxazine, pyridine, carbazine, carbocyanine iodide and others. Specific examples include ABS 574, ABS 668 or ABS 674 from Exiton, Inc.; or SDA2443, SDA3572 or ADA4863 available from H.W. Sands Corp. It is possible to use mixtures of any of the dyes mentioned above.

[0073] In another embodiment, an optical brightener is used, also called fluorescent whitening agent (FWA - Fluorescent Whitening Agent), optical brightening agent (OBA - Optical Brightening Agent) or fluorescent whitening agent (FBA - Fluorescent Brightening Agent) .

[0074] As is well known, optical brighteners are substances that absorb light in the UV and violet region (usually in 340 to 370 nm) and emit light by fluorescence essentially in the blue region of the visible spectrum (400 to 460 nm, preferably in the range from 420 to 450 nm). Preferred optical brighteners have high fluorescence efficiency, that is, they re-emit as visible light a large proportion of the energy they have absorbed.

[0075] When the optical article has front and rear main surfaces, the respective rear surface is preferably not coated with any layer containing optical brighteners.

[0076] The chemical nature of the optical brightener is not particularly limited as long as it is capable of emitting light by fluorescence, ideally a maximum fluorescence, at a wavelength ranging between 420 and 450 nm, so as to hide the yellow color transmitted by the medium optical filtering.

[0077] The optical brightener can be chosen, without limitation to these families, from stilbenes, carbostyrils, coumarins, 1,3-diphenyl-2-pyrazolines, naphthalimides, combined heteroaromatics (such as pyrenyl-triazines or other combinations of heterocyclic compounds , such as thiazoles, pyrazoles, oxadiazoles, fused polyaromatic systems or triazines, directly connected to each other or through a conjugated ring system), benzoxazoles, in particular benzoxazoles substituted in position 2 by a conjugated ring system, preferably comprising groups ethylene, phenylethylene, stilbene, benzoxazole and/or thiophene. The preferred families of optical brighteners are bis-benzoxazoles, phenylcoumarins, methylcoumarins and bis-(styryl)biphenyls, which are described in more detail in A. G. Oertli, “Plastics Additives Handbook”, 6th Edition, H. Zweifel, D. Maier, M Schiller Editors, 2009.

[0078] Other useful optical brighteners that can be used in the present invention are described in “Fluorescent Whitening agents”, Anders G. EQS, “Environmental quality and safety” (Suppl. Vol IV) Georg Thieme Stuttgart 1975. Specific examples of brighteners Commercially available optics are disclosed in WO 2015/097186, and WO2015097492 in the name of the applicant.

[0079] In systems according to the invention, the optical filtering medium and/or the color balancing medium may be incorporated into the substrate of the optical article, in at least one coating on the surface of the substrate or in a layer sandwiched between two substrate films. They can both be incorporated into the substrate, both in the same coating, e.g. ex. a primer coating, a hard coating or an anti-reflective coating, or separately in different locations, for example one on the substrate and the other on a coating deposited on one or another face of the optical article (which may be convex, concave or flat), separately in (at least) two different coatings, or a combination of these modalities can be implemented, continuing to obtain the advantages and benefits of the invention in terms of health and cosmetic appearance. For example, the optical filtering medium may be located in a hard coating, and the color balancing medium included in a primer coating, or the optical filtering medium may be included in the substrate, and the color balancing medium included in a coating. If the optical filtering medium and the color balancing medium are included in (at least) two different coatings, these coatings are not necessarily deposited on the same face of the optical article. They can be deposited on one or the other side of the optical article or on both sides of the optical article.

[0080] In one embodiment, the functionality to block blue light wavelengths and the functionality to perform color balancing are combined into a single component that blocks blue light wavelengths and reflects some green and red wavelengths.

[0081] Various optical filtering means and/or color balancing means can be incorporated into the substrate and/or into the same or different layers deposited on the surface of the substrate. In some embodiments, the optical filtering medium is divided between two filters disposed on the same or different surfaces of the optical substrate.

[0082] The optical filtering medium is preferably contained in the substrate of the optical article. Methods for incorporating an absorbent dye, a UV absorber or a color balancing means into the substrate mass of the optical article are well known and include, for example (see e.g. WO 2014/133111): i. impregnation or imbibition methods consisting of immersing the substrate in an organic solvent and/or water-based hot dye bath, preferably a water-based solution, for several minutes. Substrates made of organic materials, such as organic lens substrates, are most often colored in the bulk of the material by immersion in aqueous coloring baths, heated to temperatures in the order of 90 °C, and in which the filter medium optics or color balancing medium has been dispersed. This compound thus diffuses under the surface of the substrate, and the color density is obtained by adjusting the amount of compound diffusing into the body of the substrate, ii. the diffusion methods described in JP 2000-314088 and JP 2000241601, involving a temporary impregnable coating, iii. non-contact coloring using a sublimable material, as described in US 6534443 and US 6554873, or iv. incorporation of the compound during the manufacture of the substrate itself, for example by casting or injection molding, if it is sufficiently resistant to high temperatures present during casting or injection molding. This is preferably accomplished by mixing the compound into the substrate composition (an optical material resin or a polymerizable composition) and then forming the substrate by curing the composition in a suitable mold.

[0083] In another embodiment, the optical article comprises a substrate and at least one layer coated on the substrate, wherein the optical filtering means and/or color balancing means are incorporated into said at least one layer coated on the substrate. These compounds can be incorporated, for example, into a hard coating and/or a primer coating, which generally promotes adhesion of the hard coating to the substrate. They can also be incorporated into a film that will subsequently be transferred, laminated, fused or glued to the substrate.

[0084] Several methods familiar to those practiced in the art of optical manufacturing are known to incorporate the optical filtering medium (and/or the color balancing medium) in a layer. These compounds can be deposited at the same time as the layer, that is, when the layer is prepared from a liquid coating composition, they can be incorporated (directly or, for example, as particles impregnated by the compound) or dissolved in said coating composition. coating before it is applied (in situ mixing) and hardened on the surface of the substrate.

[0085] The optical filtering medium (and/or the color balancing medium) may also be included in a coating in a separate process or sub-process. For example, the compound can be included in the coating after its deposition on the surface of the substrate, using an immersion coloring method similar to that referred to for coloring the substrate, that is, by means of a dyebath at elevated temperatures, using the method diffusion method disclosed in US 2003/0020869, in the name of the depositor, through the method disclosed in US 2008/127432, in the name of the depositor, which uses a printing primer that is subjected to printing using an inkjet printer, through the method disclosed in US 2013/244045, in the name of the depositor, which involves printing with a sublimation dye by means of a thermal transfer printer, or through the method disclosed in US 2009/047424, in the name of the depositor, which uses a porous layer for transferring a coloring agent onto the substrate. The compound may also be sprayed onto a surface before the coating is cured (e.g., thermally or UV cured), dried or applied.

[0086] Obviously, combinations of several of the methods described above can be used to obtain an optical article having at least one optical filtering means and/or color balancing means incorporated therein.

[0087] The amount of optical filtering media used in the present invention is an amount sufficient to provide satisfactory protection against blue light, while the amount of color balancing means used in the present invention is an amount sufficient to compensate for the effect of yellowing caused by optical filtering media.

[0088] Naturally, the respective amounts of color balancing means and optical filtering means can be adapted to each other to produce a transparent and colorless element that does not have a yellow appearance. In particular, those skilled in the art should appreciate that the desired amount of color balancing means varies depending on several factors, including the nature and amount of optical filtering means used. To this end, the optimal amounts of each compound can be determined by simple laboratory experiments.

[0089] For example, optical filtration absorbent dye can be used at a level of 0.005 to 0.150% based on the weight of the coating solution, depending on the strength of the absorbent dye and the amount of protection desired. In these cases, color balancing dye(s) may be used at a level of 0.01 to 0.10% based on the weight of the coating solution, depending on the strength of the dyes. and the final color and desired transmission %. It should be understood that the invention is not limited to these ranges, and they are only provided as an example.

[0090] Obviously, the optical article according to the invention can only appear colorless if neither its substrate nor its coatings are dyed.

[0091] In some applications, it is preferred that the main surface of the substrate is coated with one or more functional coatings to improve optical and/or mechanical properties. The term "coating" is understood to mean any layer, stack of layers or film that may be in contact with the substrate and/or with another coating, for example a sol-gel coating or a coating made from an organic resin. A coating can be deposited or formed through a variety of methods, including wet processing, gaseous processing, and film transfer. Such functional coatings classically used in optics may be, without limitation, an adhesion and/or impact-resistant primer, an abrasion-resistant and/or scratch-resistant coating, an anti-reflective coating, a polarized coating, a photochromic coating, or a antistatic, or a stack made of two or more coatings, especially an impact-resistant primary coating coated with an abrasion- and/or scratch-resistant coating.

[0092] Coatings resistant to abrasion and/or scratches (hard coatings) are preferably hard coatings based on poly(meth)acrylates or silanes. The hard coatings resistant to abrasion and/or scratches recommended in the present invention include coatings obtained from compositions based on silane hydrolyzate (sol-gel process), in particular compositions based on epoxysilane hydrolyzate, such as those described in the application patent US 2003/0165698 and US 4,211,823 and EP614957.

[0093] The primary coatings improving the impact resistance and/or adhesion of the other layers in the final product are preferably polyurethane latex or acrylic latex. Abrasion-resistant and/or scratch-resistant primer coatings and coatings can be selected from those described in application WO 2007/088312.

[0094] The anti-reflective coating can be any anti-reflective coating traditionally used in the field of optics, particularly ophthalmic optics. An anti-reflective coating is defined as a coating deposited on the surface of an optical article, which improves the anti-reflective properties of the final optical article. This makes it possible to reduce light reflection at the article-air interface over a relatively large portion of the visible spectrum.

[0095] As is also well known, anti-reflective coatings traditionally comprise a single-layer or multi-layer stack composed of dielectric and/or sol-gel materials and/or organic/inorganic layers, as disclosed in WO2013098351. Preferably, these are multilayer coatings comprising layers with a high refractive index (AI) and layers with a low refractive index (BI).

[0096] In the present application, a layer of the anti-reflective coating is said to be a layer with a high refractive index when its refractive index is greater than 1.55, preferably equal to or greater than 1.6, more preferably equal to or greater to 1.8 and even more preferably equal to or greater than 2.0. A layer of an anti-reflective coating is said to be a low refractive index layer when its refractive index is equal to or less than 1.55, preferably equal to or less than 1.50, more preferably equal to or less than 1.45. Unless otherwise specified, the refractive indices referred to in the present invention are expressed at 25 °C at a wavelength of 550 nm.

[0097] Layers AI and BI are traditional layers well known in the art generally comprising one or more metal oxides, which can be chosen, without limitation, from the materials disclosed in WO 2011/080472.

[0098] Preferred AI layers comprise at least one material selected from the group consisting of zirconia (ZrO2), titanium dioxide (TiO2), tantalum pentoxide (Ta2O5), niobium oxide (Nb2O5), alumina (Al2O3), oxide praseodymium (Pr2O3), praseodymium titanate (PrTiO3), silicon nitride and silicon oxynitride.

[0099] Preferred BI layers comprise at least one oxide chosen from silicon oxide, silica, mixtures of silicon oxide and alumina. When a BI layer comprising a mixture of SiO2 and Al2O3 is used, it preferably comprises 1 to 10%, more preferably 1 to 8% and even more preferably 1 to 5% by weight of Al2O3 relative to the total weight of SiO2 + Al2O3 in this layer. The outer layer of anti-reflective coating is preferably a BI layer, more preferably a silica-based layer.

[0100] Typically, AI layers have a thickness ranging between 10 and 120 nm, and BI layers have a thickness ranging between 10 and 100 nm.

[0101] Preferably, the total thickness of the anti-reflective coating is less than 1 micron, more preferably equal to or less than 800 nm and even more preferably equal to or less than 500 nm. The total anti-reflective thickness is generally greater than 100 nm, preferably greater than 150 nm.

[0102] Even more preferably, the anti-reflective coating comprises at least two layers with a low refractive index (BI) and at least two layers with a high refractive index (AI). Preferably, the total number of layers in the anti-reflective coating is equal to or less than 8, more preferably equal to or less than 6, and most preferably equal to or greater than 4.

[0103] The AI and BI layers do not need to alternate with each other in the anti-reflective coating, although they can also, according to an embodiment of the invention. Two AI layers (or more) can be deposited on top of each other, as well as two BI layers (or more) can be deposited on top of each other.

[0104] Coatings, such as primers, hard coatings and anti-reflective coatings according to the invention, can be deposited using methods known in the art, including spin coating, dip coating, spray coating, evaporation, spraying, chemical deposition steam and lamination.

[0105] The various layers of the anti-reflective coating are preferably deposited according to any of the methods disclosed in WO 2011/080472, which is incorporated herein by reference. A particularly recommended method is vacuum evaporation.

[0106] The structure and preparation of anti-reflective coatings are also described in more detail in patent applications WO 2010/109154 and WO 2012/153072.

[0107] In one embodiment of the invention, the rear main face of the optical article, the front main face of the optical article or both are coated with an anti-reflective coating, preferably a multi-layer one, so that the light reflection factor on said face rear main and/or on said front main face in the visible region Rv is equal to or less than 2.5%.

[0108] In another embodiment of the invention, the rear main face of the optical article, the front main face of the optical article or both are coated with an anti-reflective coating, preferably a multi-layer one, so that the average reflection factor on said face main back surface and/or on said front main face in the visible region Rm is equal to or less than 2.5%.

[0109] In some aspects of the invention, the optical article has an Rv factor and/or an Rm factor equal to or less than 2%, 1.5%, 1%, 0.8% or 0.6% in at least one main face, preferably both on said rear main face and on said front main face.

[0110] The means of achieving these Rv and Rm values are well known to those skilled in the art.

[0111] Rv, which is also called “light reflection factor”, is as defined in ISO 13666:1998, and is measured in accordance with ISO 8980-4 (for an incidence angle of less than 17°, typically of 15°), that is, it is the weighted average spectral reflection across the entire visible spectrum between 380 and 780 nm.

[0112] In the present application, the “average reflection factor”, indicated as Rm, is as defined in ISO 13666:1998 and measured in accordance with ISO 8980-4 (for an angle of incidence less than 17°, typically 15°), that is, it is the average spectral reflection (unweighted) across the entire visible spectrum between 400 and 700 nm.

[0113] In the present application, the factors Rv and Rm were measured at an incidence angle of 15°.

[0114] Preferably, the anti-reflective coatings described above block less than 2.5% of light having a wavelength ranging between 420 and 450 nm reaching the front main face of the optical article, by absorption and/or reflection.

[0115] In some aspects, the present invention provides an optical article further comprising a sublayer, deposited before the anti-reflective coating, said sublayer preferably having a refractive index equal to or less than 1.55. The sublayer is generally less than 0.5 micrometers thick and more than 100 nm thick, preferably more than 150 nm thick, more preferably the sublayer thickness ranges between 150 nm and 450 nm. In another embodiment, the sublayer comprises, more preferably consists of, silicon oxide, even better silica. Examples of usable sublayers (single layer or multiple layers) are described in WO 2012/076174.

[0116] In some embodiments, the anti-reflective coating of the invention includes at least one electrically conductive layer. In a particular embodiment, the at least one electrically conductive layer has a refractive index greater than 1.55. The at least one electrically conductive layer serves as an antistatic agent. Without any connection to any theory, the at least one electrically conductive layer prevents the multi-layer anti-reflective coating stack from developing and retaining a static electrical charge.

[0117] The ability of a glass to evacuate a static charge obtained after rubbing with a piece of fabric or using any other procedure to generate a static charge (load applied per crown) can be quantified by measuring the time it takes to dissipate said charge. Thus, anti-static glasses have a discharge time of about a few hundred milliseconds (ms), preferably 500 ms or less, while a static glass is about several tons of seconds. In the present application, discharge times are measured in accordance with the method disclosed in FR 2943798.

[0118] As used herein, an “electrically conductive layer” or an “antistatic layer” is intended to mean a layer that, due to its presence on the surface of a substrate, is not antistatic (i.e., having a discharge time greater than 500 ms) , allows a discharge time of 500 ms or less after applying a static charge to the surface.

[0119] The electrically conductive layer may be located in various locations in the stack, generally on or in contact with the anti-reflective coating, as long as the respective anti-reflective properties are not affected. Preferably, it lies between two layers of the anti-reflective coating and/or is adjacent to a layer with a high refractive index of that anti-reflective coating. Preferably, the electrically conductive layer is located immediately under a layer having a low refractive index, more preferably it is the penultimate layer of the anti-reflective coating while it is preferably located immediately under a silica-based outer layer of the anti-reflective coating.

[0120] The electrically conductive layer must be thin enough not to alter the transparency of the anti-reflective coating. The electrically conductive layer is preferably made of an electrically conductive and highly transparent material, generally an optionally doped metal oxide. In this case, its thickness preferably varies from 1 to 15 nm, more preferably from 1 to 10 nm. Preferably, the electrically conductive layer comprises an optionally doped metal oxide selected from oxides of indium, tin, zinc and mixtures thereof. Indium tin oxide (In2O3:Sn, doped tin indium oxide), doped aluminum zinc oxide (ZnO:Al), indium oxide (In2O3) and tin oxide (SnO2) are preferred. In a more preferred embodiment, the electrically conductive and optically transparent layer is an indium tin oxide layer or a tin oxide layer.

[0121] The optical article of the invention is configured to reduce reflection in the range of UVA and UVB radiation, in addition to reducing reflection in the visible region, so as to allow better health protection against harmful blue light and UV.

[0122] In this regard, the optical article preferably comprises on its rear main face, and optionally on its front main face, an anti-UV anti-reflective coating having very good anti-reflective performances in the visible region, and which is at the same time capable of reducing significantly reflect the reflection of UV radiation, especially ultraviolet A and ultraviolet B rays, compared to a bare substrate or a substrate comprising a traditional anti-reflective coating.

[0123] The average RUV reflection factor on the rear main face between 280 nm and 380 nm, weighted by the W(À) function defined in ISO 13666:1998, is less than 7%, preferably less than 5%, more preferably equal or less than 4.5%, even better equal to or less than 4% for an incidence angle of 35° (on the back face). In another embodiment, the average reflection factor RUV on the rear main face between 280 nm and 380 nm, weighted by the function W(À) defined in ISO 13666:1998, is preferably less than 5% for both an angle of incidence of 30 ° as for an angle of incidence of 45°. Said average reflection factor RUV is defined through the following relationship:

[0124] where R(À) represents the spectral reflection factor of the lens at a given wavelength, and W(À) represents a weighting function equal to the product of the solar spectrum irradiation Es(À) and the spectral function relative efficiency S(À). In certain embodiments, this factor can be measured at an angle of incidence that varies between 30° and 45° on the rear face.

[0125] The spectral function W(À), allowing the calculation of ultraviolet radiation transmission factors, is defined in accordance with ISO Standard 13666:1998. This makes it possible to express the distribution of ultraviolet solar radiation tempered by the relative spectral efficiency of this radiation for the carrier, since it simultaneously takes into account the solar spectral energy Es(À), which globally emits fewer UVB rays compared to UVA, and the spectral efficiency S(À), UVB rays being more harmful than UVA rays. The values for these three functions in the ultraviolet region are given in the table revealed on page 6 of publication WO 2012/076714.

[0126] In some embodiments, the above anti-UV performances are provided by the anti-reflective coating while maintaining an Rv factor on the back main face and/or front main face equal to or less than 2.5%.

[0127] The optical article according to the invention may also comprise coatings formed in an anti-reflective coating and capable of modifying the surface properties thereof, such as hydrophobic and/or oleophobic coatings (anti-corrosive top coating). These coatings are preferably deposited on the outer layer of the anti-reflective coating. As a rule, its thickness is equal to or less than 10 nm, preferably varies between 1 and 10 nm, more preferably between 1 and 5 nm. Generally, these are fluorosilane or fluorosilazane type coatings. They can be obtained by depositing a fluorosilane or fluorosilazane precursor preferably comprising at least two hydrolysable groups per molecule. The fluorosilane precursors preferably comprise fluoropolyether moieties and more preferably perfluoropolyether moieties.

[0128] Optool DSX™, KY130™, OF210™, Aulon™ are examples of hydrophobic and/or oleophobic coatings. More detailed information about these coatings is disclosed in WO 2012076714.

[0129] The invention also relates to the use of the optical article described above to protect at least part of a user's eye against phototoxic blue light, otherwise indicated as light having a wavelength between 420 and 450 nm.

[0130] Next, particularities are presented that can be combined with the specific particularities of the invention already described in the present application.

[0131] One embodiment of the invention is an optical article comprising at least one optical filtering medium that is an absorbent dye A that selectively and at least partially blocks the transmission of light having a wavelength ranging between 400 and 500 nm, wherein dye A has an absorption peak in the range 400 nm to 460 nm and the absorption spectrum of the optical article is such that the contribution to absorption in the range 400 to 435 nm is greater than that in the range 435 to 460 nm .

[0132] In one embodiment, the absorption spectrum of the optical article is such that the ratio R1 of the area under the curve (absorption curve) from 435 to 460 nm and the area under the curve from 400 to 435 nm is less than 0.7.

[0133] In another embodiment, the absorption spectrum of the optical article is such that the ratio R1 of the area under the curve between 435 to 460 nm and the area under the curve between 400 to 435 nm is less than 0.6.

[0134] The absorption spectrum is obtained from transmittance values T of the optical article for each wavelength in the wavelength range of 380 to 780 nm measured by a spectrophotometer, and then the transmittance values of the optical article are converted into A absorbance data using the formula: A = 2 - log10 %T.

[0135] Then, the absorbance spectrum can be represented. The absorbance values of the optical article take into account all the blue blocking due to reflection at the different interfaces (especially at the substrate/air interface) and the absorption due to the materials of the optical article (substrate materials, coatings). A spectrophotometer can also be programmed to provide direct absorbance values.

[0136] Preferably, dye A has an absorption peak in the range of 400 nm to 428 nm, preferably in the range of 415 nm to 428 nm.

[0137] Preferably, dye A has an absorption peak that exhibits a half-height width equal to or less than 40 nm.

[0138] Preferably, the optical article comprises at least one color balance dye B having an absorption peak at a wavelength equal to or greater than 500 nm, B preferably being an anthraquinone.

[0139] Preferably, dye A has a specific absorption coefficient greater than 200 L.g-1.cm-1 in methylene chloride, preferably greater than 300 L.g- 1.cm-1, more preferably greater than 400, 500, 600 L.g-1.cm-1.

[0140] Preferably, the optical article has an absorption spectrum such that the ratio R2 of the area under the curve from 460 to 700 nm and the area under the curve from 400 to 460 nm is equal to or less than 2.25.

[0141] The following examples illustrate the present invention in a more detailed, but not limiting, manner. Unless otherwise indicated, all thicknesses disclosed in the present application relate to physical thicknesses.

Examples

[0142] The optical articles used in the examples comprise an ESSILOR ORMA® lens substrate having a diameter of 65 mm, a refractive index of 1.50, a power of -2.00 diopters and a thickness of 1.2 mm , coated on the front side with a coating comprising an absorbent dye or a UV absorber for at least partially inhibiting light having a wavelength ranging between 420 and 450 nm, and a second dye functioning as a color balancing means. The concentration of these dyes was adjusted to obtain the desired b* and a* colorimetric coefficients and the desired level of blue light blocking in the range of 420 to 450 nm. The blue light-blocking dye provided a selectively absorbing optical filtering medium. Said dye had an absorption peak centered at about 421 nm, with a half-height width (LMA) of less than 40 nm. Table 1 - Coating compositions including filtration media.

[0143] On this 12 μm thick coating incorporating the optical filtering medium and optionally the color balancing medium, an 8 μm thick intermediate coating was deposited as described in example 1 Table 1 of US7,410,691.

[0144] Next, an impact-resistant polyurethane primer coating (W234™) with a thickness of about 1 μm was deposited, in that order, on the intermediate coating, an abrasion-resistant coating corresponding to example 3 of EP614957 of about 2.5 μm and an anti-reflective coating comprising a SiO2 sublayer with a thickness of 150 nm, a ZrO2 layer with a thickness of 28 nm, a SiO2 layer with a thickness of 22 nm, a ZrO2 layer with a thickness of 72 nm, an antistatic layer with a thickness of 6 nm composed of indium tin oxide and a layer of SiO2 with a thickness of 84 nm.

[0145] The rear main face of the lens was only coated with the W234™ primary layer, the abrasion-resistant coating as described above and the anti-UV anti-reflective coating comprising a SiO2 sublayer with a thickness of 150 nm, a ZrO2 layer with a thickness of 19 nm, a SiO2 layer with a thickness of 23 nm, a ZrO2 layer with a thickness of 93 nm, an antistatic layer with a thickness of 6.5 nm composed of indium tin oxide and a layer of SiO2 with a thickness of 82 nm. Said coating has an Rv of 0.59% and an RUV of 2.59% at 30° and 3.1% at 45°.

Optical performances

[0146] The optical performances of the lenses were measured using a Hunter UltraScan Pro spectrophotometer and are shown in the table below, where % blue cut (420 to 450 nm) represents the % of light blocked having a wavelength ranging between 420 and 450 nm reaching the front main face of the optical article. % blue cutoff (420 to 450 nm) = 100 - % average transmission at 420 to 450 nm.

[0147] The results show that the optical articles according to the invention selectively block at least 10% of harmful blue light (420 to 450 nm), transmit at least 94.5% of the blue light involved in circadian rhythms (465 to 495 nm) and reflect very little UV radiation resulting from light sources situated behind the wearer towards the wearer's eye (low UVR at an oblique incidence). Sensory analysis

[0148] The lenses as prepared above were evaluated by a panel of 15 trained judges having at least one view to have a rating of 0.8 on the Monoyer test (i.e., being able to read the 0.8 line). .

[0149] The rooms where sensory analyzes are carried out comply with the AFNOR NF V 09-15 standard. The ISO 13299:2003 standard is used. Judges are selected and trained in accordance with the ISO8586 standard.

[0150] The lighting in the rooms corresponds to D65 lighting. Likewise, the points of light correspond to white light.

[0151] The methodology used is as follows: 1) comparative presentation of the samples, 2) evaluation of the products in a random order (Latin Squares) to avoid disturbances due to the order effect, 3) the products are anonymous and are identified only by a 3 digit code.

[0152] The lens transparency criterion was studied from the point of view of the wearer or observer.

Lens (carrier) transparency

[0153] Definition: which allows light to pass through and allows the wearer's eyes to appear clearly.

[0154] Protocol: the wearer looks in the mirror and evaluates the transparency of the lens by observing whether they can see their eyes clearly. Scale: from 0 (not transparent) to 10 (very transparent).

Lens transparency (observer)

[0155] Definition: which allows light to pass through and allows the wearer's eyes to appear clearly.

[0156] Protocol: The evaluator looks at a person in front of him and evaluates the transparency of the lens by observing whether the person's eyes are clearly seen. Scale: from 0 (not transparent) to 10 (very transparent).

[0157] In the table below, the lens of the invention protects the wearer against UV and blue risk while being sufficiently transparent, except comparative 1, in which the notation with respect to transparency is very low. It is surprising to see that lenses having lower transmission are nevertheless seen as more transparent by the wearer than lenses having higher transmission but higher b*.

Claims (13)

1. Optical article comprising a substrate having a front main face and a rear main face, defined as: - having a colorimetric coefficient b* as defined in the CIE L*a*b* colorimetric system (1976) which is equal to or less than 7 , - having a relative light transmission factor in the visible spectrum Tv greater than or equal to 87%, - blocking at least 8% to 30% of light having a wavelength varying between 420 and 450 nm reaching said front main face, - having an average reflection factor RUV on said rear main face between 280 nm and 380 nm, weighted by the W(À) function defined in ISO 13666:1998, less than 7% for an angle of incidence of 35°, characterized by fact that the optical article comprises at least: - an optical filtering medium, which is an absorbent dye that selectively and at least partially blocks the transmission of light having a wavelength ranging between 400 and 500 nm, wherein the dye A has an absorption peak: - in the range of 415 nm to 428 nm, and - exhibits a full width at half height of 40 nm or less, and the absorption spectrum of the optical article is such that the contribution to absorption in the range of 400 to 435 nm is higher than in the range of 435 to 460 nm, - a color balance dye B having an absorption peak at a wavelength equal to or greater than 500 nm, and said rear main face and said front main face are coated with a multi-layer anti-reflective coating, the average light reflection factor on said rear main face and said front main face in the visible region Rv being equal to or less than 2.5%. 2. Optical article according to claim 1, characterized by the fact that it is further defined as transmitting at least 95% of light having a wavelength ranging between 465 and 495 nm. 3. Optical article according to any one of claims 1 or 2, characterized by the fact that it has a relative light transmission factor in the visible spectrum Tv ranging between 87% and 98.5%, preferably between 87% and 97% , more preferably between 87% and 96%. 4. Optical article according to any one of claims 1, 2 or 3, characterized by the fact that it is further defined as blocking at least 12% of the light having a wavelength ranging between 420 and 450 nm reaching said main face front. 5. Optical article according to claim 1, characterized by the fact that dye A is ABS420. 6. Optical article according to any one of claims 1 to 5, characterized in that said multi-layer anti-reflective coatings block less than 2.5% of light having a wavelength ranging between 420 and 450 nm reaching the front main face. 7. Article according to any one of claims 1 to 6, characterized by the fact that it has an average light reflection factor in the visible region Rv equal to or less than 0.6% on at least one main face. 8. Article according to any one of claims 1 to 7, characterized by the fact that it has an average light reflection factor in the visible region Rv less than or equal to 0.6% on said rear main face and on said main face front. 9. Optical article according to any one of claims 1 to 8, characterized by the fact that the average reflection factor RUV on said rear main face between 280 nm and 380 nm, weighted by the function W(À) defined in the ISO standard 13666:1998, is less than 5%, preferably less than 3%, both for an incidence angle of 30° and for an incidence angle of 45°. 10. Optical article according to any one of claims 1 to 9, characterized by the fact that it has a colorimetric coefficient a* as defined in the international colorimetric system L*a*b* CIE (1976) which is less than or equal to 3 . 11. Optical article according to any one of claims 1 to 10, characterized by the fact that it has a colorimetric coefficient a* as defined in the international colorimetric system L*a*b* CIE (1976) which is greater than or equal to - 5 and preferably varies between -5 and -1. 12. Optical article according to any one of claims 1 to 11, characterized by the fact that it has a colorimetric coefficient b* as defined in the international colorimetric system L*a*b* CIE (1976) which is equal to or less than 3 . 13. Optical article according to any one of claims 1 to 12, characterized by the fact that it is further defined as an ophthalmic lens.